High-temperature reactivity of vanadium oxide clusters in methane activation: Vibrational degrees of freedom matter.

Abstract

Understanding the properties of small particles working under high-temperature conditions at the atomistic scale is imperative for exact control of related processes, but it is quite challenging to achieve experimentally. Herein, benefitting from state-of-the-art mass spectrometry and by using our newly designed high-temperature reactor, the activity of atomically precise particles of negatively charged vanadium oxide clusters toward hydrogen atom abstraction (HAA) from methane, the most stable alkane molecule, has been measured at elevated temperatures up to 873K. We discovered the positive correlation between the reaction rate and cluster size that larger clusters possessing greater vibrational degrees of freedom can carry more vibrational energies to enhance the HAA reactivity at high temperature, in contrast with the electronic and geometric issues that control the activity at room temperature. This finding opens up a new dimension, vibrational degrees of freedom, for the simulation or design of particle reactions under high-temperature conditions.